A family of chiral iminophenyl oxazolinylphenylamines (IPOPA) ligands enables an efficient cobalt-catalyzed asymmetric hydrosilylation of simple ketones with a low catalyst loading of CoCl2 to afford chiral alcohols in good yields with high enantioselectivities.
X. Chen, Z. Lu, Org. Lett., 2016, 18, 4658-4661.
A zinc-catalyzed reduction of tertiary amides shows remarkable chemoselectivity and substrate scope tolerating ester, ether, nitro, cyano, azo, and keto substituents.
S. Das, D. Addis, S. Zhou, K. Junge, M. Beller, J. Am. Chem. Soc., 2010, 132, 1770-1771.
Transition-metal-free catalytic protocols for controlled reduction of amide functions using cheap and bench-stable hydrosilanes as reducing agents enable the selective reduction of unactivated C-O bonds in amides. By altering the hydrosilane and solvent, the C-N bonds selectively breaks via a deacylative cleavage.
W. Yao, L. He, D. Han, A. Zhong, J. Org. Chem., 2019, 84, 14627-14635.
A simple, mild, catalyst-free, and efficacious KOtBu-mediated reductive cyanation reaction of tertiary amides provides a series of α-aminonitriles in good yields under hydrosilylation conditions with good functional group tolerance. The reaction works well with readily available amide substrates, cheap KOtBu, and a commercially available hydrosilane (EtO)3SiH and the workup is convenient.
L . Liu, Y. Liu, X. Shen, X. Zhang, S. Deng, Y. Chen, J. Org. Chem., 2022, 87, 6321-6329.
A highly regio- and enantioselective copper-catalyzed reductive hydroxymethylation of styrenes and 1,3-dienes with 1 atm of CO2 readily provides important chiral homobenzylic alcohols. Moreover, various 1,3-dienes were converted to chiral homoallylic alcohols with high yields and excellent regio-, enantio-, and Z/E-selectivities.
Y.-Y. Gui, N. Hu, X.-W. Chen, L-L. Liao, J.-H. Ye, Z. Zhang, J. Li, D.-G. Yu, J. Am. Chem. Soc., 2017, 139, 17011-17014.
A nickel hydride-catalyzed hydroacylation of aryl alkenes using aroyl fluorides proceeds without recourse to an exogenous ligand under mild conditions. The synthetic utility of the present method is demonstrated by a glovebox-free, gram-scale reaction and late-stage derivatizations of complex molecules.
J. Kim, J. Jang, Y. Lee, K. Shin, Org. Lett., 2022, 24, 5412-5416.
An enantioselective Ni-catalyzed reaction of an alkyl halide (derived from an aldehyde and an acyl bromide), an olefin, and a hydrosilane provides esters of chiral dialkyl carbinols. The method is versatile and tolerates substituents that vary in size and that bear a range of functional groups. A four-component variant of this process, wherein the alkyl halide is generated in situ, is also reported.
Z.-P. Yang, G. C. Fu, J. Am. Chem. Soc., 2020, 142, 5870-5875.
An efficient rhodium-catalyzed method allows the preparation of aryltriethoxysilanes from arenediazonium tosylate salts. A new method for hydrodediazoniation has also been explored.
Z. Y. Tang, Y. Zhang, T. Wang, W. Wang, Synlett, 2010, 804-808.
A bimetallic catalyst system composed of a group 4 metallocene difluoride and palladium dichloride enables a reductive cross-coupling of alkynes and aryl halides to provide (E)-alkenes in the presence of a hydrosilane and NaF. This reaction proceeds via an in situ generated alkenyl metallocene intermediate derived from the group 4 metallocene difluoride.
K. Takahashi, H. Morishita, Y. Ogiwara, N. Sakai, J. Org. Chem., 2018, 83, 13734-13742.